Fungicidal Mixtures

ABSTRACT

Fungicidal mixtures comprising, as active components, 
 
1) a triazolopyrimidine derivative of the formula I,  
                 
in which the variables are as defined below: 
         R 1  is alkyl, haloalkyl or alkenyl;    R 2  is hydrogen or one of the groups mentioned for R 1 ;    R 1  and R 2  together may also form a straight-chain or branched alkylene chain; L is fluorine, chlorine or bromine; m is 2 or 3; and 2) one or more inhibitors of gibberellin biosynthesis (II) and/or auxin transport (III); in a synergistically effective amount, methods for controlling harmful fungi using mixtures of compounds of the formula I with inhibitors II and/or III by using the mixtures according to the invention and the use of the compound I with inhibitors II and/or III for preparing such mixtures, and also compositions comprising these mixtures.

The present invention relates to fungicidal mixtures comprising, asactive components,

1) a triazolopyrimidine derivative of the formula I,

-   -   in which the variables are as defined below:    -   R¹ is C₁-C₆-alkyl, C₁-C₆-haloalkyl or C₃-C₆-alkenyl;    -   R² is hydrogen or one of the groups mentioned for R¹;    -   R¹ and R² together may also form a straight-chain or branched        C₃-C₈-alkylene chain;    -   L is fluorine, chlorine or bromine;    -   m is 2 or 3;

and

2) one or more inhibitors of gibberellin biosynthesis (II) and/or auxintransport (III);

in a synergistically effective amount.

Moreover, the invention relates to a method for controlling harmfulfungi using mixtures of compounds of the formula I and inhibitors IIand/or III by using the mixtures according to the invention and the useof the compounds I with inhibitors II and/or III for preparing suchmixtures, and also to compositions comprising these mixtures.

The compounds of the formula I, their preparation and their actionagainst harmful fungi are known from the literature (EP-A 550 113; WO98/46607; WO 98/46608).

The inhibitors II and/or III are generally known in agriculture asgrowth regulators. They relate in particular to active compounds fromthe groups:

-   -   acylcyclohexanedione compounds of the formula IIa    -   in which    -   R is hydrogen, C₁-C₈-alkyl, C₁-C₈-alkylthioalkyl or phenyl which        is unsubstituted or substituted by one to three groups R^(a) and        -   R^(a) is halogen, nitro, cyano, amino, C₁-C₈-alkyl,            C₁-C₄-haloalkyl, C₁-C₈-alkoxy or C₁-C₄-haloalkoxy,    -   G is C₁-C₈-alkyl, C₃-C₆-cycloalkyl, benzyl which is        unsubstituted or substituted in the ring system by one to three        groups R^(a), is phenethyl, phenoxymethyl, 2-thienylmethyl,        C₁-C₈-alkoxymethyl or C₁-C₈-alkylthiomethyl steht,    -   and agriculturally tolerable salts thereof;    -   triazolyls (IIb) as inhibitors of cytochrome P-450-dependent        monooxygenases whose principal action is to block the metabolism        of gibberellins, such as paclobutrazol (IIb.1) or uniconazole        (IIb.2);    -   quaternary ammonium compounds (IIc) which inhibit early        reactions in gibberellin biosynthesis, in particular chlormequat        chloride (IIc.1), mepiquat chloride (IIc.2) and mepiquat        pentaborate (IIc.3);    -   and also    -   inhibitors of auxin transport (III), in particular        2-{1-[4-(3,5-difluorophenyl)semicarbazono]ethyl}nicotinic acid,        common name diflufenzopyr (III.1).

In modern agriculture, the efficacy of fungicides is still hampered bythe following problems:

-   -   unsatisfactory action against individual parasite species which        are generally less sensitive to certain active compounds;    -   unsatisfactory action against individual pathogen strains which        have developed resistance against or tolerance to certain        fungicidally active compounds;    -   unsatisfactory action against attack by harmful fungi, owing to        excessively low penetration of the crop stand with fungicide        spray mist.

In many cases, the tolerance or resistance of harmful fungi tofungicides is the result of an incomplete application of fungicides.Especially in dense crop stands or in dense crowns of fruit trees,treatment by spraying or atomizing does not reach the inner regions ofthe stands or individual plants, or only reaches them in part. As aresult, there are areas which are not or only partially protectedagainst fungal attack. In the latter case, there is the risk thatstrains of harmful fungi are formed and then widely propagate which aretolerant or resistant to the fungicides employed, which massivelyreduces the benefit of such agents.

Accordingly, it was an object of the invention to provide activecompound combinations having improved action against harmful fungi,reducing the probability of the harmful fungi becoming tolerant orresistant to the fungicidally active compounds.

Surprisingly, it has now been found that, by using fungicidally activecompounds of the formula I and growth regulators of the formulae II andIII simultaneously, it is much easier to prevent plant damage caused bypathogens in a large number of agricultural and horticultural cropplants than by a fungicide treatment only with compounds of the formulaI. Moreover, it has been found that simultaneous, that is joint orseparate, application of the compound I and the inhibitors II/III orsequential application of the compound I and the inhibitors II/IIIallows better control of harmful fungi than the individual compounds(synergistic mixtures). The direct result are increased yields combinedwith a better quality of the harvested material.

The inhibitors II and III mentioned, their preparation and their actionare known per se from the prior art:

prohexadione, usually employed in the form of an alkali metal oralkaline earth metal salt, in particular as calcium salt:prohexadione-Ca (IIa.1): EP-A 123 001;

trinexapac, usually employed as ester or salt; in particular as theethyl ester: trinexapac-ethyl (IIa.2): EP-A 126 713;

paclobutrazol (IIb.1): Proc. Br. Crop Prot. Conf.—Weeds, 1982, Vol.1, p.3;

uniconazole (IIb.2): Plant Cell Physiol., 1984, Vol. 25, p. 611;

chlormequat, usually employed in the form of a salt, such as thechloride: chlormequat chloride (IIc.1): US 3 156 554; DE 11 99 048;

mepiquat, usually employed in the form of a salt, such as the chloride:mepiquat chloride (IIc.2) or pentaborate: mepiquat pentaborate (IIc.3):U.S. Pat. No. 3,905,798; DE 22 07 575.

diflufenzopyr (III.1), is frequently also employed in the form of asalt, such as the sodium salt: Proc. Br. Crop Prot. Conf.—Weeds, 1999,Vol.1, p. 35.

Particularly suitable growth regulators are acylcyclohexanediones of theformula IIa, such as prohexadione-Ca (IIa.1) or trinexapac-ethyl(IIa.2), since, in addition to their morphoregulatory action, they arealso able to protect crop plants against biotic and abiotic stressors[cf.: EP-A 123 001, page 27, lines 20 and 21 (for prohexadione andrelated substances) or for trinexapac-ethyl and related compounds inEP-A 126 713]. The induction of resistance by the compounds mentionedagainst certain pathogens is known from Bazzi et al. (European Journalof Horticultural Science 68; pp. 108-114; pp. 115-122).

The use of diflufenzopyr of the formula III.1 optimizes not only theefficacy of fungicides but also leads to an increased yield in usefulplants (WO 01/43544).

Fungicidal mixtures of 5-chlorotriazolopyrimidines with fungicidallyactive compounds are known in a general manner from EP-A 988 790 andU.S. Pat. No. 6,268,371.

Suitable for the mixtures according to the invention are in particularthose compounds of the formula I in which R¹ and R² together form astraight-chain or branched C₃-C₈-alkylene chain. These compoundscorrespond to formula I.1,

where D is a straight-chain or branched C₃-C₈-alkylene chain, inparticular a branched C₅-alkylene chain, such as 3-methylpentylene.

Preference is likewise given to compounds of the formula I in which thesubstituted 6-phenyl group is a 2,4,6-trifluorophenyl ring. Thesecompounds correspond to formula I.2,

where R¹ and R² are as defined for formula I.

In addition, the invention also preferably provides the followingembodiment of the compounds of the formula I:

In formula I.3, Y is hydrogen or methyl.

Particular preference is given to the following compounds of the formulaI: No. R¹ R² L_(m) I-1 —CH₂CH₂CH(CH₃)CH₂CH₂— 2,4,6-F₃ I-2—CH₂CH₂CH(CH₃)CH₂CH₂— 2-F,6-Cl I-3 (S)CH(CH₃)CF₃ H 2,4,6-F₃

The compound I-1,5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidineis especially preferred for use in the mixtures according to theinvention.

The mixtures of the compound I and the inhibitors II and/or III or thesimultaneous, that is joint or separate, use of the compound I and theinhibitors II and/or III are distinguished by being highly activeagainst a wide range of phytopathogenic fungi, in particular from theclasses of the Ascomycetes, Deuteromycetes, Oomycetes andBasidiomycetes. They can be used in crop protection as foliarfungicides, as fungicides for seed dressing and as soil-actingfungicides.

They are particularly important for controlling a multitude of fungi onvarious cultivated plants, such as bananas, cotton, vegetable species(for example cucumbers, beans and cucurbits), barley, grass, oats,coffee, potatoes, corn, fruit species, rice, rye, soybeans, tomatoes,grapevines, wheat, ornamental plants, sugar cane and on a large numberof seeds.

They are particularly suitable for the control of the followingphytopathogenic fungi: Blumeria graminis (powdery mildew) on cereals,Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits,Podosphaera leucotricha on apples, Uncinula necator on grapevines,Puccinia species on cereals, Rhizoctonia species on cotton, rice andlawns, Ustilago species on cereals and sugar cane, Venturia inaequalison apples, Bipolaris and Drechslera species on cereals, rice and lawns,Septoria species on wheat, Botrytis cinerea on strawberries, vegetables,ornamental plants and grapevines, Mycosphaerella species on bananas,peanuts and cereals, Pseudocercosporella herpotrichoides on wheat andbarley, Pyricularia oryzae on rice, Phakopsora species on soybeans,Phytophthora infestans on potatoes and tomatoes, Pseudoperonosporaspecies on cucurbits and hops, Plasmopara viticola on grapevines,Alternaria species on fruit and vegetables and also Fusarium andVerticillium species.

Particularly advantageously, they are suitable for the treatment oflignescent plants (in particular fruit species and grapevines), and alsoseedlings (vegetables and strawberries from the families of theSolanaceae and Rosaceae) and ornamental plants.

The compound I and the inhibitors II and/or III can be appliedsimultaneously, that is jointly or separately, or in succession, where,in the case of separate application, the inhibitors II and/or III arepreferably applied first.

When preparing the mixtures, it is preferred to employ the pure activecompounds I and II/III, to which further active compounds againstharmful fungi or against other pests, such as insects, arachnids ornematodes, or else herbicidal or growth-regulating active compounds orfertilizers can be added according to need.

Other suitable active compounds in the above sense are in particularfungicides selected from the following groups:

-   -   acylalanines, such as benalaxyl, metalaxyl, ofurace, oxadixyl,    -   amine derivatives, such as aldimorph, dodine, dodemorph,        fenpropimorph, fenpropidin, guazatine, iminoctadine,        spiroxamine, tridemorph,    -   anilinopyrimidines, such as pyrimethanil, mepanipyrim or        cyprodinil,    -   antibiotics, such as cycloheximid, griseofulvin, kasugamycin,        natamycin, polyoxin or streptomycin,    -   azoles, such as bitertanol, bromoconazole, cyproconazole,        difenoconazole, dinitroconazole, enilconazole, epoxiconazole,        fenbuconazole, fluquinconazole, flusilazole, flutriafol,        hexaconazole, imazalil, ipconazole, metconazole, myclobutanil,        penconazole, propiconazole, prochloraz, prothioconazole,        simeconazole, tebuconazole, tetraconazole, triadimefon,        triadimenol, triflumizol, triticonazole,    -   dicarboximides, such as iprodione, myclozolin, procymidone,        vinclozolin,    -   dithiocarbamates, such as ferbam, nabam, maneb, mancozeb, metam,        metiram, propineb, polycarbamate, thiram, ziram, zineb,    -   heterocyclic compounds, such as anilazine, benomyl, boscalid,        carbendazim, carboxin, oxycarboxin, cyazofamid, dazomet,        dithianon, famoxadone, fenamidone, fenarimol, fuberidazole,        flutolanil, furametpyr, isoprothiolan, mepronil, nuarimol,        penthiopyrad, picobenzamid, probenazole, proquinazid, pyrifenox,        pyroquilon, quinoxyfen, silthiofam, thiabendazole, thifluzamid,        thiophanate-methyl, tiadinil, tricyclazole, triforine,    -   copper fungicides, such as Bordeaux mixture, copper acetate,        copper oxychloride, basic copper sulfate,    -   nitrophenyl derivatives, such as binapacryl, dinocap, dinobuton,        nitrophthalisopropyl,    -   phenylpyrroles, such as fenpiclonil or fludioxonil,    -   sulfur,    -   other fungicides, such as acibenzolar-S-methyl, benthiavalicarb,        carpropamid, chlorothalonil, cyflufenamid, cymoxanil,        diclomezine, diclocymet, diethofencarb, edifenphos, ethaboxam,        fenhexamid, fentin acetate, fenoxanil, ferimzone, fluazinam,        fosetyl, fosetyl-aluminum, iprovalicarb, hexachlorobenzene,        mandipropamid, metrafenone, pencycuron, propamocarb, phosphorous        acid, phthalide, toloclofos-methyl, quintozene, zoxamide,    -   strobilurins, such as azoxystrobin, dimoxystrobin, enestroburin,        fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin,        picoxystrobin, pyraclostrobin or trifloxystrobin,    -   sulfenic acid derivatives, such as captafol, captan,        dichlofluanid, folpet, tolylfluanid,    -   cinnamides and analogous compounds, such as dimethomorph,        flumetover or flumorph.

In one embodiment of the mixtures according to the invention, a furtherfungicide IV or two fungicides IV and V are added to the compounds I andII/III.

Preference is given to mixtures of the compounds I and II/III and acomponent IV. Particular preference is given to mixtures of thecompounds I and II or III.

What is usually used are mixtures of a compound I with an inhibitor IIor III. In certain cases, however, mixtures of a compound with two ormore inhibitors II and/or III may be advantageous.

The compound I and the inhibitors II are usually applied in a weightratio of from 100:1 to 1:100, preferably from 20:1 to 1:20, inparticular from 10:1 to 1:10. The compound I and the inhibitors III, inparticular the compound III.1, are usually applied in a weight ratio offrom 1000:1 to 1:1, preferably from 200:1 to 20:1.

The components IV and, if appropriate, V are, if desired, added in aratio of from 20:1 to 1:20 to the compound I.

Depending on the type of compound and the desired effect, theapplication rates of the mixtures according to the invention are from 5g/ha to 1000 g/ha, preferably 50 to 900 g/ha, in particular 50 to 750g/ha.

Correspondingly, the application rates for the compound I are generallyfrom 1 to 1000 g/ha, preferably from 10 to 900 g/ha, in particular from20 to 750 g/ha.

Correspondingly, the application rates for the inhibitors II aregenerally from 1 to 1000 g/ha, preferably from 10 to 900 g/ha, inparticular from 40 to 750 g/ha.

Correspondingly, the application rates for the inhibitors III, inparticular the compound III.1, are generally from 0.01 to 50 g/ha,preferably from 0.1 to 10 g/ha.

In the treatment of seed, application rates of mixture are generallyfrom 1 to 1000 g/100 kg of seed, preferably from 1 to 750 g/100 kg, inparticular from 5 to 500 g/100 kg.

The method for controlling harmful fungi is carried out in agriculturalcrops by the separate or joint application of the compound I and theinhibitors II and/or III or of the mixtures of the compound I and theinhibitors II and/or III, by spraying or dusting the seeds, the plantsor the soils before or after sowing of the plants or before or afteremergence of the plants. In permanent crops such as fruit trees orgrapevines, the treatment is preferably carried out before or during theannual growth phase.

The mixtures according to the invention, or the compounds I and II/III,can be converted into the customary formulations, for example solutions,emulsions, suspensions, dusts, powders, pastes and granules. The useform depends on the particular intended purpose; in each case, it shouldensure a fine and even distribution of the compound according to theinvention.

The formulations are prepared in a known manner, for example byextending the active compound with solvents and/or carriers, if desiredusing emulsifiers and dispersants. Solvents/auxiliaries suitable forthis purpose are essentially:

-   -   water, aromatic solvents (for example Solvesso products,        xylene), paraffins (for example mineral oil fractions), alcohols        (for example methanol, butanol, pentanol, benzyl alcohol),        ketones (for example cyclohexanone, gamma-butyrolactone),        pyrrolidones (NMP, NOP), acetates (glycol diacetate), glycols,        fatty acid dimethylamides, fatty acids and fatty acid esters. In        principle, solvent mixtures may also be used,    -   carriers such as ground natural minerals (for example kaolins,        clays, talc, chalk) and ground synthetic minerals (for example        highly disperse silica, silicates); emulsifiers such as        nonionogenic and anionic emulsifiers (for example        polyoxyethylene fatty alcohol ethers, alkylsulfonates and        arylsulfonates) and dispersants such as lignosulfite waste        liquors and methylcellulose.

Suitable surfactants used are alkali metal, alkaline earth metal andammonium salts of lignosulfonic acid, naphthalenesulfonic acid,phenolsulfonic acid, dibutylnaphthalenesulfonic acid,alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcoholsulfates, fatty acids and sulfated fatty alcohol glycol ethers,furthermore condensates of sulfonated naphthalene and naphthalenederivatives with formaldehyde, condensates of naphthalene or ofnaphthalenesulfonic acid with phenol and formaldehyde, polyoxyethyleneoctylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol,alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether,tristearylphenyl polyglycol ether, alkylaryl polyether alcohols, alcoholand fatty alcohol ethylene oxide condensates, ethoxylated castor oil,polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, laurylalcohol polyglycol ether acetal, sorbitol esters, lignosulfite wasteliquors and methylcellulose.

Substances which are suitable for the preparation of directly sprayablesolutions, emulsions, pastes or oil dispersions are mineral oilfractions of medium to high boiling point, such as kerosene or dieseloil, furthermore coal tar oils and oils of vegetable or animal origin,aliphatic, cyclic and aromatic hydrocarbons, for example toluene,xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or theirderivatives, methanol, ethanol, propanol, butanol, cyclohexanol,cyclohexanone, isophorone, highly polar solvents, for example dimethylsulfoxide, N-methylpyrrolidone and water.

Powders, materials for spreading and dustable products can be preparedby mixing or concomitantly grinding the active substances with a solidcarrier.

Granules, for example coated granules, impregnated granules andhomogeneous granules, can be prepared by binding the active compounds tosolid carriers. Examples of solid carriers are mineral earths such assilica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk,bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate,magnesium sulfate, magnesium oxide, ground synthetic materials,fertilizers, such as, for example, ammonium sulfate, ammonium phosphate,ammonium nitrate, ureas, and products of vegetable origin, such ascereal meal, tree bark meal, wood meal and nutshell meal, cellulosepowders and other solid carriers.

In general, the formulations comprise from 0.01 to 95% by weight,preferably from 0.1 to 90% by weight, of the active compounds. Theactive compounds are employed in a purity of from 90% to 100%,preferably from 95% to 100% (according to NMR spectrum).

The following are examples of formulations: 1. Products for dilutionwith water

A) Water-Soluble Concentrates (SL)

10 parts by weight of the active compounds are dissolved in water or ina water-soluble solvent. As an alternative, wetters or other auxiliariesare added. The active compound dissolves upon dilution with water.

B) Dispersible Concentrates (DC)

20 parts by weight of the active compounds are dissolved incyclohexanone with addition of a dispersant, for examplepolyvinylpyrrolidone. Dilution with water gives a dispersion.

C) Emulsifiable Concentrates (EC)

15 parts by weight of the active compounds are dissolved in xylene withaddition of calcium dodecylbenzenesulfonate and castor oil ethoxylate(in each case 5% strength). Dilution with water gives an emulsion.

D) Emulsions (EW, EO)

40 parts by weight of the active compounds are dissolved in xylene withaddition of calcium dodecylbenzenesulfonate and castor oil ethoxylate(in each case 5% strength). This mixture is introduced into water bymeans of an emulsifying machine (Ultraturrax) and made into ahomogeneous emulsion. Dilution with water gives an emulsion.

E) Suspensions (SC, OD)

In an agitated ball mill, 20 parts by weight of the active compounds arecomminuted with addition of dispersants, wetters and water or an organicsolvent to give a fine active compound suspension. Dilution with watergives a stable suspension of the active compound.

F) Water-Dispersible Granules and Water-Soluble Granules (WG, SG)

50 parts by weight of the active compounds are ground finely withaddition of dispersants and wetters and prepared as water-dispersible orwater-soluble granules by means of technical appliances (for exampleextrusion, spray tower, fluidized bed). Dilution with water gives astable dispersion or solution of the active compound.

G) Water-Dispersible Powders and Water-Soluble Powders (WP, SP)

75 parts by weight of the active compounds are ground in a rotor-statormill with addition of dispersants, wetters and silica gel. Dilution withwater gives a stable dispersion or solution of the active compound.

2. Products to be Applied undiluted

H) Dustable Powders (DP)

5 parts by weight of the active compounds are ground finely and mixedintimately with 95% of finely divided kaolin. This gives a dustableproduct.

I) Granules (GR, FG, GG, MG)

0.5 part by weight of the active compounds is ground finely andassociated with 95.5% carriers. Current methods are extrusion,spray-drying or the fluidized bed. This gives granules to be appliedundiluted.

J) ULV Solutions (UL)

10 parts by weight of the active compounds are dissolved in an organicsolvent, for example xylene. This gives a product to be appliedundiluted.

The active compounds can be used as such, in the form of theirformulations or the use forms prepared therefrom, for example in theform of directly sprayable solutions, powders, suspensions ordispersions, emulsions, oil dispersions, pastes, dustable products,materials for spreading, or granules, by means of spraying, atomizing,dusting, spreading or pouring. The use forms depend entirely on theintended purposes; they are intended to ensure in each case the finestpossible distribution of the active compounds according to theinvention.

Aqueous use forms can be prepared from emulsion concentrates, pastes orwettable powders (sprayable powders, oil dispersions) by adding water.To prepare emulsions, pastes or oil dispersions, the substances, as suchor dissolved in an oil or solvent, can be homogenized in water by meansof a wetter, tackifier, dispersant or emulsifier. However, it is alsopossible to prepare concentrates composed of active substance, wetter,tackifier, dispersant or emulsifier and, if appropriate, solvent or oil,and such concentrates are suitable for dilution with water.

The active compound concentrations in the ready-to-use preparations canbe varied within relatively wide ranges. In general, they are from0.0001 to 10%, preferably from 0.01 to 1%.

The active compounds may also be used successfully in theultra-low-volume process (ULV), it being possible to apply formulationscomprising over 95% by weight of active compound, or even to apply theactive compound without additives.

Oils of various types, wetters, adjuvants, herbicides, fungicides, otherpesticides, or bactericides may be added to the active compounds, even,if appropriate, not until immediately prior to use (tank mix). Theseagents are typically admixed with the compositions according to theinvention in a weight ratio of from 1:10 to 10:1.

The compounds I and II/III or the mixtures or the correspondingformulations are applied by treating the harmful fungi, the plants,seeds, soils, areas, materials or spaces to be kept free from them witha fungicidally effective amount of the mixture or, in the case ofseparate application, of the compounds I and II. Application can becarried out before or after infection by the harmful fungi.

The fungicidal effect of the compound and the mixtures can bedemonstrated by the following tests:

The active compounds, separately or jointly, were prepared as a stocksolution comprising 0.25% by weight of active compound in acetone orDMSO. 1% by weight of the emulsifier Uniperol® EL (wetting agent havingemulsifying and dispersant action based on ethoxylated alkylphenols) wasadded to this solution, and the mixture was diluted with water to thedesired concentration.

USE EXAMPLE 1 Activity Against Scab on Apple Leaves Caused by Venturiainaequalis, Protective Application

Leaves of apples were sprayed to runoff point with an aqueous suspensionhaving the concentration of active compound stated below. After 12 days,the treated plants were inoculated with an aqueous spore suspension ofVenturia inaequalis. The apples were then initially placed in awater-vapor-saturated chamber at 24° C. for 48 hours and then in agreenhouse at temperatures between 20 and 24° C. for 20 days. The extentof the development of the infection on the upper sides of the leaves wasthen determined visually.

The visually determined percentages of infected leaf areas wereconverted into efficacies in % of the untreated control:

The efficacy (E) is calculated as follows using Abbot's formula:E=(1−α/β)−100

α corresponds to the fungal infection of the treated plants in % and

β corresponds to the fungal infection of the untreated (control) plantsin %

An efficacy of 0 means that the infection level of the treated plantscorresponds to that of the untreated control plants; an efficacy of 100means that the treated plants were not infected.

The expected efficacies of mixtures of active compounds were determinedusing Colby's formula (Colby, S. R. “Calculating synergistic andantagonistic responses of herbicide Combinations”, Weeds, 15, 20-22,1967) and compared with the observed efficacies.

Colby's formula:E=x+y−x·y/100

E expected efficacy, expressed in % of the untreated control, when usingthe mixture of the active compounds A and B at the concentrations a andb

x efficacy, expressed in % of the untreated control, when using theactive compound A at the concentration a

y efficacy, expressed in % of the untreated control, when using theactive compound B at the concentration b TABLE A Individual activecompounds Concentration of active compound Efficacy in % Activecompound/ in the spray of the untreated Example Mixing ratio liquor[ppm] control 1 control (untreated) — (92% infection) 2 I-1 50 48 25 183 prohexadione-Ca (IIa.1) 100 29 50 4

TABLE B Mixtures according to the invention Mixture of active compoundsConcentration Observed Calculated Example Mixing ratio efficacyefficacy*) 4 I-1 + IIa.1 73 50  50 + 50 ppm 1:1 5 I-1 + IIa.1 78 63 50 +100 ppm 1:2 6 I-1 + IIa.1 73 42 25 + 100 ppm 1:4*)calculated efficacy using Colby's formula

USE EXAMPLE 2 Activity Against Peronospora of Grapevines Caused byPlasmopara viticola, 9 Day Protective Application

Leaves of potted vines were sprayed to runoff point with an aqueoussuspension having the concentration of active compound stated below. Tobe able to assess the persistency of the substances, the plants were,after the spray coating had dried on, placed in a greenhouse for 9 days.Only then were the leaves inoculated with an aqueous zoospore suspensionof Plasmopara viticola. The grapevines were then initially placed in awater-vapor-saturated chamber at 24° C. for 48 hours and then in agreenhouse at temperatures between 20 and 30° C. for 5 days. After thistime, the plants were again placed in a humid chamber for 16 hours, topromote sporangiophore eruption. The extent of the development of theinfection on the undersides of the leaves was then determined visually.

Evaluation was carried out analogously to example 1. TABLE C Individualactive compounds Concentration of active compound Efficacy in % Activecompound/ in the spray of the untreated Example Mixing ratio liquor[ppm] control 7 control (untreated) — (80% infection) 8 I-1 50 25 25 139 Prohexadione-Ca (IIa.1) 100 0 50 0

TABLE D Mixtures according to the invention Mixture of active compoundsConcentration Observed Calculated Example Mixing ratio efficacyefficacy*) 10 I-1 + IIa.1 63 25  50 + 50 ppm 1:1 11 I-1 + IIa.1 75 2550 + 100 ppm 1:2 12 I-1 + IIa.1 69 13 25 + 100 ppm 1:4*)calculated efficacy using Colby's formula

USE EXAMPLE 3 Activity Against Net Blotch of Barley Caused byPyrenophora teres, 1 Day Protective Application

Leaves of potted barley seedlings of the cultivar “Hanna” were sprayedto runoff point with an aqueous suspension having the concentration ofactive compound stated below. 24 hours after the spray coating had driedon, the test plants were inoculated with an aqueous spore suspension ofPyrenophora [syn. Drechslera] teres, the net blotch pathogen. The testplants were then placed in a greenhouse at temperatures between 20 and24° C. and at 95 to 100% relative atmospheric humidity. After 6 days,the extent of the development of the disease was determined visually in% infection of the entire leaf area.

Evaluation was carried out analogously to example 1. TABLE E Individualactive compounds Concentration of active compound Efficacy in % Activecompound/ in the spray of the untreated Example Mixing ratio liquor[ppm] control 13 control (untreated) — (89% infection) 14 I-1 3.1 66 15chlormequat chloride 3.1 0 (IIc.1) 6.3 0 16 diflufenzopyr (III.1) 0.0310

TABLE F Mixtures according to the invention Mixture of active compoundsConcentration Observed Calculated Example Mixing ratio efficacyefficacy*) 17 I-1 + IIc.1 83 66 3.1 + 3.1 ppm 1:1 18 I-1 + IIc.1 89 663.1 + 6.3 ppm 1:2 19 I-1 + III.1 83 66 3.1 + 0.031 ppm  100:1 *)calculated efficacy using Colby's formula

The results show that, by virtue of strong synergism, the mixturesaccording to the invention are considerably more effective in all mixingratios than had been predicted using Colby's formula.

1. A fungicidal mixture for controlling phytopathogenic harmful fungi,which mixture comprises 1) a triazolopyrimidine derivative of theformula I,

in which the variables are as defined below: R¹ is C₁-C₆-alkyl,C₁-C₆-haloalkyl or C₃-C₆-alkenyl; R² is hydrogen or one of the groupsmentioned for R¹; R¹ and R² together may also form a straight-chain orbranched C₃-C₈-alkylene chain; L is fluorine, chlorine or bromine; m is2 or 3; and 2) one or more inhibitors of gibberellin biosynthesis (II)selected from acylcyclohexanedione compounds of the formula Ia

in which R is hydrogen, C₁-C₈-alkyl, C₁-C₈-alkylthioalkyl or phenylwhich is unsubstituted or substituted by one to three groups R^(a) andR^(a) halogen, nitro, cyano, amino, C₁-C₈-alkyl, C₁-C₄-haloalkyl,C₁-C₈-alkoxy or C₁-C₄-haloalkoxy may be substituted, G is C₁-C₈-alkyl,C₃-C₆-cycloalkyl, benzyl which is unsubstituted or substituted in thering system by one to three groups R^(a), is phenethyl, phenoxymethyl,2-thienylmethyl, C₁-C₈-alkoxymethyl or C₁-C₈-alkylthiomethyl, andagriculturally tolerable salts thereof; triazolyls (IIb) as inhibitorsof cytochrome P-450-dependent monooxygenases whose principal action isto block the metabolism of gibberellins; quaternary ammonium compounds(llc) which inhibit early reactions in gibberellin biosynthesis; and/orinhibitors of auxin transport (III) in a synergistically effectiveamount.
 2. The fungicidal mixture according to claim 1 comprising thetriazolopyrimidine derivative I-1


3. The fungicidal mixture according to claim 1 comprising, as inhibitor(ll), an active compound selected from the group consisting ofprohexadione-Ca (IIa.1); trinexapac-ethyl (IIa.2); paclobutrazol(IIb.1); uniconazole (IIb.2); chlormequat chloride (IIc.1); mepiquatchloride (llc.2) and mepiquat pentaborate (llc.3).
 4. The fungicidalmixture according to claim 1 comprising, as inhibitor (III),2-{1-[4-(3,5-difluorophenyl)semicarbazono]ethyl}nicotinic acid,diflufenzopyr (lll.1).
 5. The fungicidal mixture according to claim 1comprising the compound of the formula I and an inhibitor II in a weightratio of from 100:1 to 1:100.
 6. The fungicidal mixture according toclaim 1 comprising the compound of the formula I and an inhibitor III ina weight ratio of from 1000:1 to 1:1.
 7. A composition comprising aliquid or solid carrier and a mixture according to claim
 1. 8. A methodfor controlling phytopathogenic harmful fungi which comprises treatingthe fungi, their habitat or the seed, the soil or the plants to beprotected against fungal attack with a synergistically effective amountof the compounds I and II and/or III according to claim
 1. 9. The methodaccording to claim 8, wherein the compounds I and II and/or IIIaccording to any of claims 1 to 4 are applied simultaneously, that isjointly or separately, or in succession.
 10. The method according toclaim 8, wherein the compounds I and II and/or III according to claim 1or the mixtures according to any of claims 1 to 6 are applied in anamount of from 5 g/ha to 1000 g/ha.
 11. The method according to claim 8,wherein the compounds I and II and/or III according to claim 1 or themixtures according to any of claims 1 to 6 are applied in an amount offrom 1 to 1000 g/ 00 kg of seed.
 12. Seed comprising the mixtureaccording to claim 1 in an amount of from 1 to 1000 g/100 kg.
 13. Theuse of the compounds I and II and/or III according to claim 1 forpreparing a composition suitable for controlling harmful fungi.
 14. Thefungicidal mixture according to claim 2 comprising, as inhibitor (ll),an active compound selected from the group consisting of prohexadione-Ca(IIa.1); trinexapac-ethyl (IIa.2); paclobutrazol (IIb.1); uniconazole(IIb.2); chlormequat chloride (IIc.1); mepiquat chloride (llc.2) andmepiquat pentaborate (llc.3).
 15. The fungicidal mixture according toclaim 2 comprising, as inhibitor (lIl), 2-{1-[4-(3,5-difluorophenyl)semicarbazono]ethyl}nicotinic acid, diflufenzopyr(lll.1).
 16. The fungicidal mixture according to claim 2 comprising thecompound of the formula I and an inhibitor II in a weight ratio of from100:1 to 1:100.
 17. The fungicidal mixture according to claim 3comprising the compound of the formula I and an inhibitor II in a weightratio of from 100:1 to 1:100.
 18. The fungicidal mixture according toclaim 2 comprising the compound of the formula I and an inhibitor III ina weight ratio of from 1000:1 to 1:1.
 19. The fungicidal mixtureaccording to claim 4 comprising the compound of the formula I and aninhibitor III in a weight ratio of from 1000:1 to 1:1.
 20. A compositioncomprising a liquid or solid carrier and a mixture according to claim 2.